Theoretical analysis uncovers a novel outer-sphere mechanism for C(sp2)–H activation in Pd-catalyzed reactions, suggesting new avenues for C–H functionalization.
The density functional theory (DFT) study reveals a novel mechanism for Pd‐catalyzed C(sp 2 )−H activation through an unconventional outer‐sphere deprotonation pathway. The canonical β ‐hydride elimination in alkenyl‐Pd systems has been unequivocally demonstrated to be both kinetically and thermodynamically unfavorable. Our computational analysis reveals this energetic penalty stems from three key factors: (1) increased ring strain in the four‐membered transition state, (2) stronger Pd‐C bonding due to π‐backdonation in alkenyl‐Pd species, and (3) thermodynamic instability of the resulting Pd‐H intermediate. This work elucidates a general mechanism for overcoming the longstanding challenge of β ‐C(sp 2 )−H activation in alkenyl‐metal systems, providing new insights for future development of C–H functionalization reactions.
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Zhang et al. (2025) studied this question.
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